Appl. Phys. A 72, 475479 (2001) / Digital Object Identifier (DOI) 10.
1007/s003390000537
Pulsed-laser-induced transformation path of graphite to diamond via
an intermediate rhombohedral graphite
G.W. Yang1,2, , J.B. Wang1
1 Department of Physics, Xiangtan University, Xiangtan 411105, P.R. China
2 Department of Material Science and Engineering, Tsinghua University, Beijing 100084, P.R. China
Received: 7 February 2000/Accepted: 28 March 2000/Published online: 9 November 2000
Abstract. The new phase transformation of hexagonal graph-
ite to cubic diamond was experimentally produced without
catalyst, using a high-power pulsed laser. Interestingly, by
the X-ray diffraction spectra, it was proved that this transi-
tion was not direct, but through an intermediate rhombohedral
phase. Furthermore, it is important that the rhombohedral
phase, as the theoretical transformation path of hexagonal
graphite to cubic diamond, was first truly substantiated by
our experimental results. The transformation mechanism was
suggested that diamond with hexagonal structure was ob-
tained by the direct transforming of hexagonal graphite to
hexagonal diamond, and diamond with cubic structure was
formed by the indirect transforming, i.e., hexagonal graphite
to rhombohedral graphite to cubic diamond.
PACS: 42.62.-b; 81.05.Tp; 81.30.Dz
Diamond has great science and technical applications, due to
its unique combinations of physical and chemical properties,
thus, the interests in preparation of diamond are drastically
motivated. The investigation of the dense phase of carbon,
for example, graphite and diamond, and mechanisms that un-
derlie their mutual transformation is a long-standing problem
of great fundamental importance. Although hexagonal graph-
ite (hex-g) is known to be the most stable phase of carbon at
ambient conditions, a large activation barrier prevents cubic
diamond (cub-d) from transforming to graphite. Considering
that the high-pressure region of the carbon phase diagram
is instead dominated by diamond [1], the high temperature
and high pressure (HTHP) was first used to achieve the con-
version of graphite to diamond. This transition takes place
in the pressuretemperature region of 5 GPa to 12 GPa and
2000 K to 3000 K in the carbon phase diagram, and cata-
lysts such as some transition metals aid the conversion [2].
The shock-wave (SW) can also induce the conversion of
graphite to diamond without catalyst, which takes place at
Corresponding author.
(Fax: 86-10-732-8292-468, E-mail: G_W_Yang@263.net)
Applied Physics A
Materials
Science & Processing
Springer-Verlag 2000
the pressure of 15 GPa and temperature of 1000 K [3], and
the hexagonal diamond (hex-d) so-called Lonsdaleite, as the
metastable phase with respect to cub-d, was first prepared by
shock-wave [4]. Meanwhile, Bundy also obtained the hex-d
by using the static high-pressure pressing the hex-g along the
c axis at the high temperature [5]. However, recent attempts
to reproduce the conversion of graphite to hex-d under static
pressure failed [6, 7], it is therefore so far not completely
confirmed that the conversion of graphite to hex-d could be
achieved under static high-pressure. Very recently, it had been
demonstrated that fullerite crystals built up by C60 molecules
were transformed to diamond at the pressure of 20 GPa and
ambient temperature [810].
For the theoretical side, the highly symmetric transform-
ation path from rhombohedral graphite (rh-g) to cub-d was
first considered, i.e., rh-g as an intermediate phase of hex-g
to cub-d transformation [11, 12], and the transformation path
would lead a final [111] diamond orientation parallel to the
original graphite c axis. These deductions were in agreement
with the catalyst-aided conversion in HTHP [5], in which cat-
alyst was suggested to aid the mutual orientation formation
of hex-g and cub-d [13]. The orthorhombic graphite (or-g)
was also considered to be the transformation path of hex-g
to cub-d and hex-d [14, 15], and this path would lead to the
final [112] diamond orientation parallel to the c axis of the
hex-g, similar to the shock-wave experimental results [16].
Considering a large activation barrier from graphite to dia-
mond, we would like to know whether the intermediate phase
with metastable structure as the transformation path would
exist in the conversion of graphite to diamond. However, to
our knowledge, to date, the existence of the hypothesized
intermediate phase, i.e., rh-g and or-g, in the conversion of
graphite to diamond has never been truly substantiated by
the direct experiments [11, 17, 18]. To gain a better under-
standing of the conversion of graphite to diamond, we re-
port a new transition of graphite to diamond without catalyst
by employing a high-power pulsed laser. It is very interest-
ing that a rh-g phase, the intermediate phase as the trans-
formation path of graphite to diamond, was observed in the
experiment.
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1 Experimental procedure

A high-power pulsed laser was employed to induce the con-

version of graphite to diamond, which was named pulsed-
laser-induced liquidsolid interfacial quenching (PLIIQ) [19].
The experimental system was described as follows. The sec-
ond harmonic was produced by a Q-switched Nd:YAG laser
with wavelength = 532 nm, pulse width = 10 nm, repe- Fig. 1a,b. The morphology and the corresponding selected area electron
tition frequency = 5 Hz, power density P = 1010 W cm2 , diffraction pattern of the prepared diamond crystals. a A single diamond
which means that pulsed laser energy can vary in the range grain whose size is about 300 nm, and it is an intergrowth crystal which has
of 200 mJ to 350 mJ. The target was spectroscopically pure both hexagonal and cubic structure. b A corresponding SAD pattern
polycrystalline graphite. During the experiment, a target was
first fixed in the bottom of the glass chamber, then the twice-
distilled water is poured slowly into the chamber until the
target is covered by 12 mm liquid. The laser beam is focused
by a quartz lens and finally guided by a reflection mirror
onto the graphite target. The target and liquid were kept at
room temperature. When the experiment had been running for
30 min, the powders in the liquid were collected for analysis.
All analyzed samples were prepared under the same condi-
tions. Transmission electron microscopy (TEM) and X-ray
diffraction (XRD) with a copper K source were employed
to analyze the structure of the obtained samples. It is noticed
that there are two advantageous features of PLIIQ [20]. First,
no metal catalysts are used to aid the phase transformation.
Second, PLIIQ is a very fast and far from equilibrium pro-
cess, so that all metastable and stable phases forming at the
initial, intermediate and final stages of the conversion could
be reserved in the final products, especially, for the metastable
intermediate phase. In other words, the quenching times of
PLIIQ are so short that the metastable phase forming at the
intermediate stage of the conversion could be frozen in the
obtained final products. However, HTHP and SW methods
can not simultaneously have the two features (the quenching
times of SW are much longer than those of PLIIQ). It is there- Fig. 2. The corresponding indexing of the SAD pattern, B=[112],
fore very unlikely that these possible metastable intermediate B=[1010]. One sees that the hexagonal diamond and cubic diamond are
phases in the conversion of graphite to diamond could remain intermixed in the crystallites investigated here, and the orientation between
in the two methods, because these phases maybe transform these two phases is [110]c ||[1210]h , [111]c ||[0001]h and [112]c ||[1010]h
into the stable phase at the final stage. Therefore, PLIIQ pro-
vides a good experimental method to detect the intermediate
phase forming in the conversion of graphite to diamond, if diamond would increase with the used pulsed laser energy in-
these phases are existing. creasing. In addition, the conversion of graphite to diamond
was achieved by various radiated pulsed laser energies from
250 mJ to 350 mJ. To detect the possible metastable interme-
diate phase, the pulsed lasers having energy values of 280 mJ,
2 Experimental results and discussions 300 mJ, and 330 mJ were employed to produce the conversion
of graphite to diamond, respectively. The samples obtained
2.1 Conversion of graphite to diamond by various pulsed energies were analyzed by XRD. Figure 3
shows the corresponding X-ray diffraction spectra (XDS). In
The diamond crystals with good morphology are shown in the XDS of the graphite target in Fig. 3, one can see that
Fig. 1a. One can see the crystalline planes and very regular that all the diffraction peaks belong to the hex-g, and the
morphology clearly, and as evidenced by the corresponding diffraction lines of the rh-g are not found. However, with the
selected-area electron diffraction (SAD) pattern displayed in used laser energy increasing, the remarkable diffraction peaks
Fig. 1b. Based on the SAD pattern, the obtained structure was of the rh-g were clearly observed in the XDS of the sam-
identified to be of a mixture of a cubic and hexagonal dia- ple prepared by employing the 330-mJ laser. The strongest
mond phase, Fig. 2 shows the indexing of the SAD. The cubic (003) diffraction line, 2 = 26.6 , of the rh-g overlaps the
and hexagonal phases of diamond were intermixed in the strongest (005) diffraction line of the hex-g, and the second
crystallites investigated here, and the oriented relationship be- strongest (101) diffraction peak of the rh-g, 2 = 43.44 , was
tween these two phases was [110]c||[1210]h, [111]c||[0001]h, in between the hex-g (101) and hex-g (102) lines. These ex-
and [112]c||[1010]h. It is noticed that the ratio of diamonds perimental results only show the experimental evidence that
to whole powders increases with the pulsed laser energy in- the metastable rh-g phase indeed formed in the conversion of
creasing, which means the transition probability of graphite to graphite to diamond upon PLIIQ. To gain further insight into

Fig. 3a,b. X-ray diffraction spectra (XDS) of the prepared samples by
PLIIQ. a The XDS of the original solid graphite target. b The XDS of the
powders obtained by employing 330-mJ pulsed laser
the transformation of the intermediate phase rh-g, the sec-
ond strongest (101) diffraction of the rh-g was selected as the
mark line to study the dependence of intensity of the mark
line on the used laser energy. The results are shown in Fig. 4.
One clearly sees that the intensity of the (101) diffraction
peak of the rh-g rapidly increases with the used laser energy
increasing. This observation means that the transformation
probability of the hex-g to rh-g increases with the used pulsed
laser energy values increasing. Therefore, the above experi-
mental results indicate two important evidences. First, ex-
cluding the metal catalyst effect, the conversion of graphite to
diamond was strikingly confirmed upon PLIIQ. Second, the
metastable rh-g phase as the intermediate phase in the hex-g
to cub-d conversion was firmly obtained in this experiment.
2.2 Structural model of graphite-to-diamond transition
From the experimental observations above, the formation
mechanism of two structural diamonds suggested that hex-g
would be directly transformed to hex-d, however, cub-d was
obtained by an indirectly transforming, i.e., from hex-g first
to an intermediate phase rh-g, then to the final state cub-d
by a solidsolid diffusionless transformation manner [20].
Figure 5 shows this structural evolution. In other words, the
basal planes of the hex-g could become boat-buckled and di-
477
Fig. 4. The dependence of the (101) diffraction peak of the rhombohedral
graphite on various used pulsed laser energies
Fig. 5. Geometric path for graphite-to-diamond transformation: hexagonal
graphite rhombohedral graphite cubic diamond; the different stack-
ings of the hexagonal planes are viewed along the sideways
rectly yield the hex-d, whose new c axis is parallel to the ini-
tial c axis of the hex-g. Alternatively, the graphite planes first
slide towards the rh-g stacking, then the stacking planes could
become chair-buckled and yield the cub-d, whose [111] axis
is parallel to the initial c axis of the hex-g (Fig. 5). The new
c axis of the hex-d is therefore parallel to the [111] direction
of the cub-d. The role of the metastable rh-g in the conver-
sion of graphite-to-diamond is an intermediate phase, i.e., the
result of the highly symmetric path of graphite-to-diamond
transformation hypothesized by theory [11]. Based on the
structural model, the experimental results of the oriented re-
lationship between two diamond phases and hex-g was well
in agreement with the theoretical predication by hypothesized
rh-g as the intermediate phase in the graphite-to-diamond
transformation [11, 12]. In addition, from the structural model
and experimental observation above, it is suggested that the
transforming probability of hex-g to rh-g taking place in the
conversion of hex-g to cub-d would increase with the used
pulsed laser energy increasing upon PLIIQ. Therefore, it is
deduced that the ratio of rh-g to the prepared samples should
also increase with the used laser energy increasing if the
intermediate phase rh-g could be remained. Obviously, the
deduction was also well in agreement with the experimental
result (Fig. 4).
2.3 Carbon phase diagram analysis
A thermodynamic analysis of the graphite-to-diamond transi-
tion could aid the understanding of the various transformation
478
paths. From the studies of the effect of a high-power laser ir-
radiating on the surface of a solid graphite target by Venkate-
san et al. [21], the pressure dependence of the temperature of
the carbon cluster in the conversion of graphite to diamond
upon PLIIQ [20] can be determined by T = 0.1163P 2 +
15.66P + 4000, in which T is in Kelvin and P in kbar. Thus,
in our experimental studies, the range of the temperature was
deduced to be within 3500 K to 4000 K, and the range of the
pressure was deduced to be within 10 GPa to 15 GPa, in the
conversion of graphite to diamond upon PLIIQ [22]. Based on
the understanding from experimental observations through-
out 1994, Bundy provided a new pressuretemperature phase
diagram of carbon [23], as shown in Fig. 6. The solid lines
represent equilibrium phase boundaries, and the solid line
from low temperature and low pressure to the triple point
(12 GPa, 5000 K) of diamond, graphite and liquid carbon is
the so-called BermanSimon line (BS line) in the phase
diagram. From Fig. 6, one can see that diamond is in the
metastable state in the region above the BermanSimon line,
and the A region (512 GPa, 20003000 K) is the pressure
temperature region utilized for HTHP commercial prepar-
ation of diamond from graphite. It is noticed that a conversion
of graphite to diamond via the rh-g intermediate phase as
a transformation path seems to exist in this region [5]. The B
region (15 GPa, 1000 K) represents the conversion of graph-
ite to diamond via an or-g intermediate phase as the trans-
formation path found in SW. Furthermore, we mainly paid
attention to the C region (1015 GPa, 35004000 K) in the
PT phase diagram, in which the pure conversion of graphite
to diamond via a rh-g transformation path could be achieved
upon PLIIQ. Our previous studies showed that the transform-
ation probabilities of the carbon atoms over a potential barrier
to transform diamond structure in these regions above were
different [22]. For A, B, and C regions, the transiting proba-
bilities of C region are the highest, and in turn the transiting
probabilities of B region are lowest. Based on the analysis
above, it is suggested that two conversions of graphite to di-
amond, i.e. or-g and rh-g transformation paths, could exist in
B and C regions in the carbon phase diagram, respectively.
Fig. 6. The carbon phase diagram. A region: HTHP, B region: SW, C region:
PLIIQ
Since the parallelism of the [111] orientation of the fi-
nal cub-d with the c axis of the initial hex-g was found
in the catalyst-aided conversion of graphite to diamond by
HTHP [24], the model of the rh-g transformation path seems
to find the experimental evidence. However, the use of the
metal catalysts is known to drastically decrease the transiting
pressure and temperature, and is therefore expected to al-
ter significantly the conversion mechanism (possibly through
a metal-induced buckling of the graphite basal planes) [13].
However, in our results, the graphite-to-diamond conversion
was more pure, i.e., there were not any metal catalysts, the
observations in this study were therefore the true experimen-
tal evidences of the above model. Considering the conversion
of graphite to diamond upon PLIIQ taking place in C region
of the carbon phase diagram, it is suggested that the hex-g to
rh-g to cub-d phase transformation may not be achieved in
A region if the transition metal catalysts are not used.
The parallelism of the [112] orientation of the final cub-d
with the c axis of the initial hex-g was found in SW-induced
graphite-to-diamond conversion, which takes place in B re-
gion. It is therefore believed to be the experimental proof
of the theoretical model of the graphite-to-diamond conver-
sion through an or-g path, but the or-g phase had never
been obtained in the corresponding experiment [13]. Inter-
estingly, using the constant-pressure ab initio molecular dy-
namic simulations recently confirmed this model [25]. From
these results, again, it is suggested that the different graphite-
to-diamond conversions may exist in the different pressure
temperature regions in the carbon phase diagram [23], for
example, the two mentioned above. However, it is not com-
prehensible why the transforming by the rh-g path never
appeared in Scandolo et al. simulation [25]. According to
HTHP, SW, and PLIIQ, a reasonable deduction was that the
important factor about the conversion of graphite to diamond,
i.e. the temperature, was not considered in their simulations.
In other words, the temperature did not play a relevant role
due to the overwhelming effect of the pressure in the molecu-
lar dynamic simulations. In fact, the pressure of SW-induced
conversion (B region) is not much larger than that of the pres-
sures of HTHP (A region) and PLIIQ (C region), but the
temperatures of the conversions upon HTHP and PLIIQ are
much higher than that of SW. Therefore, for the conversion of
graphite to diamond, the pressure favorably induces an or-g
transformation path, then the temperature favorably produces
a rh-g transformation path.
3 Conclusion
A new conversion of graphite to diamond via a metastable
intermediate rhombohedral graphite phase as a transform-
ation path, taking place in C region of the carbon phase di-
agram, was observed by employing a pulsed-laser-induced
liquidsolid interface quenching. The experimental evidences
about the existence of the intermediate rhombohedral graph-
ite phase forming in the conversion were obtained. The hy-
pothesized structural model of the conversion of graphite to
diamond through a rhombohedral graphite path was truly
confirmed, due to the rhombohedral graphite phase and the
mutual orientation of crystals before and after transition
found. It is suggested that the conversion of graphite to dia-

mond in C region of carbon phase diagram could be mainly
induced by temperature.
Acknowledgements. The authors are grateful to the National Natural Science
Foundation of China and Natural Science Foundation of Hunan Province of
the Peoples Republic of China.
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